Process of producing p-phenylene diamines



Patented Sept. 3, 1946 PROCESS OF PRODUCING P-PHENYLENE DIAMINES Ilmari F. Salminen and Arnold Weissberger, Rochester, N. Y., assignors to Eastman Kodak Company, Rochester, N. Y., a corporation of New Jersey No Drawing. Application June 8, 1944,

Serial No. 539,398

6 Claims.

This invention relates to p-phenylene diamines and particularly to N-benzoyl-N'-acylaceto-pphenylene diamines and to their preparation.

This application is a continuation-in-part of our application Serial No. 464,892 filed November 7, 1942, now Patent 2,359,332, granted October 3, 1944.

It is an object of this invention to provide a method for obtaining valuable p-phenylene diamine derivatives. A further object is to provide compounds useful as couplers in color-forming processes of color photography.

These objects are accomplished by the provision of compounds having the following probable structure:

in which R. is an aryl radical, such as phenyl or N-benzoyl-N-benzoyl-aceto-p-phenylenediamine lOHa (N-benzoyl-N-methyl-N-benzoylaceto)-p-phenylenediamine (N-p-methylbenzoyl-N-phenyl-N'-benzoylaceto)-p-phenylenediamine cmnO-o ONH N-p-sec.-amy1benzoy1-N-acetylacetop-phenylenediamine NH-C 0 Q1120 O CH:

I 2 V V 7.

0511.100 ONHONH-CO oroooQ N-p-sec.-amylbenzoyl-N'-beuzoylaceto p-phenylenediamine C HnOC oNHQivH-ooomcoQoom N-p-sec.-amylbenzoyl-N'-anisoylaceto-pphenylenediamlne (kHnO-C ON-O-NH-C 0 011.0 00

(N-p-sec.-amylbenzoyl-N-allryl-N-benzoylaceto)-p-phenylenedlamme Our compounds may be prepared by condensation of the suitable benzoyl chloride with the suitable amine alone or in the presence of alkyline agents, such as sodium acetate, pyridine etc. The benzoyl chlorides are readily available or may be prepared in any suitable manner. For example, p-seoondary amylbenzoyl chloride may be prepared from secondary amylbenzene and acetic anhydride or acetyl chloride by condensation in a Friedel-Crafts reaction to an acetophenone. The acetophenone is then oxidized with sodium hypochlorite to p-secondary amylbenzoic acid, and this is converted by means of phosphorous trichloride or thionyl chloride to the acid chloride. l

As a specific illustration of the method of preparing our compounds, Np-secondary-amylbenzoyl-N'-benzoy1 aceto-p-phenylenediamine may be produced as follows:

(sw lling-0001 To a stirred solution of 6.9 grams (0.05 mole) of p-nitroaniline in 30 cc. of dry quinoline was added 10.5 grams of p-sec.-amylbenzoy1 chloride.

The temperature of the mixture rose spontaneously to 60, and the solution was then heated on a steam bath for two hours. After standing overnight at room temperature, the solution was poured into 500 cc. of 5% cold hydrochloric acid. The organic layer was extracted with 100 cc. of ether. The ether layer was washed successively with dilute hydrochloric acid, water, dilute sodium carbonate and with water again. The ether extract was dried, and concentrated to a viscous, yellow oil.

Ni camQ-c ONHQN o.

can-Q ONHQ-NHQCH 01 The oil wa dissolved in 100 cc. of ethyl alcohol and reduced with Raney nickel in the Adams shaker at an initial pressure of 40 lbs/sq. in. and at 90-100. It required about six hours for the absorption of the correct amount of hydrogen. The catalyst was filtered off, and the hydrochloride was isolated by carefully adding concentrated hydrochloric acid to the cold alcoholic solution. The yield was 8.0 grams (53%). The product did not have a sharp melting point; it slowly decomposed above 200.

canto-o ONHONH-1+G1HiOzC onloooam a canoe ONH-Q-NHC 0 cmc o Ca5+ CzH5O H Eight and one tenth grams (0.03 mole) of 4- (4' sec.-amylbenzamido) aniline hydrochloride was suspended in 200 cc. of 2% alkali and extracted with 100 cc. of benzene. The benzene extract was washed with dilute sodium carbonate, then thoroughly with water and the solution dried with calcium chloride. Then 25 cc. of Xylene was added and the benzene was distilled off.

In the meantime, 6 cc. of ethyl benzoylacetate in 25 cc. of xylene was heated to 150 in a 50 cc. flask connected through an 8-inch steamjacketed column to a downward water-cooled conzoyl chloride in place of p-secondary amyl benzoyl chloride.

Compound 2 is similarly prepared using benzoyl chloride in place of p-secondary amyl benzoyl chloride, and p-nitromethylam'line in place of p-nitroaniline.

Compound 3 is similarly prepared using p-toluyl chloride in place of benzoyl chloride, and i-nitrodiphenyl amine in place of p-nitroaniline.

Compound 4 is similarly prepared using ethyl acetyl acetate in place of ethyl benzoyl acetate.

Our compounds contain an active methylene group attached to carbonyl groups, by reason of which they are active in dye-forming reactions. They are especially useful in dye-forming reactions in which they combine with oxidized p-phenylene diamines to produce azomethine dyes.

It will be understood that the foregoing examples and specific embodiments of the invention are illustrative only and that the invention is not limited thereby except as indicated in the appended claims.

We claim:

1. A compound having the following formula:

where R is an aryl radical, R" is selected from the class consisting of hydrogen and hydrocarbon groups, and R, is selected from the class consisting of alkyl and aryl groups.

2. A compound having the following formula:

where R is an aryl radical and R is selected from the class consisting of alkyl and aryl groups.

3. A compound having the following formula:

where R is selected from the class consisting of alkyl and aryl groups.

4. A compound having the following formula:

where R is selected from the class consisting of alkyl and aryl groups.

5. A compound having the following formula:

O0 ONHGNH-C o cHlc 0O 6. A compound having the following formula:

05111100 ONH-O-NH-C 0 c1120 00 ILMARI F. SALMINEN. ARNOLD WEISSBERGER. 

